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The limitation of the test lies in its inability to differentiate between the biologically
oxidizable and biologically inert material and to find out the system rate constant of aerobic
biological stabilization.
Most of the organic matters are-destroyed when boiled with a mixture of potassium
dichromate and sulphuric acid producing carbon dioxide and water. A sample is refluxed with a
known amount of potassium dichromate in sulphuric acid medium and the excess of dichromate
is titrated against ferrous ammonium sulphate. The amount of dichromate consumed is
proportional to the oxygen required to oxidize the oxidizable organic matter.
SELECTION OF METHODS
There are two methods available for COD determination namely open reflux and closed
reflux.
This method is conducted with ampules and culture tubes with pre-measured
reagents.
Measurement of sample volume and reagent volume are critical.
Page 2
This method is economical in the use of metallic salt reagents and generate
smaller quantity of hazardous wastes.
Volatile organic compounds (VOC) gets completely oxidized in a closed system
than the open because of longer contact time with oxidants.
Chemical Reactions:
REAGENTS:
Standard Potassium dichromate (K2Cr2O7) digestion solution, 0.01667M:
Add to about 500 mL distilled water 4.903 g K2Cr2O7, primary standard grade,
previously dried at 150C for 2 h, 167 mL conc. H2SO4, and 33.3 g HgSO4. Dissolve,
cool to room temperature, and dilute to 1000 mL.
Add H2SO4 at the rate of 5.5 g Ag2SO4/kg H2SO4 or 10.12 g silver sulphate/L
H2SO4. Let stand 1 to 2 d to dissolve and mix. This accelerates the oxidation of straight-
chain aliphatic and aromatic compounds.
(1 Kg = 543.47826 mL of H2 SO4 and take 20.24 g of Ag2SO4 to 2 L of H2
SO4 or 22.264 g of Ag2SO4 to 2.2 L of H2 SO4)
PROCEDURE:
1. Wash culture tubes and caps with 20% H2SO4 before using to prevent contamination.
2. Place sample (2.5 mL) in culture tube and Add K2Cr2O7 digestion solution (1.5 mL).
3. Carefully run sulphuric acid reagent (3.5 mL) down inside of vessel so an acid layer is
formed under the sample-digestion solution layer and tightly cap tubes or seal ampules,
and invert each several times to mix completely.
4. Place tubes in block digester preheated to 150C and reflux for 2 h behind a protective
shield.
5. Cool to room temperature and place vessels in test tube rack. Some mercuric sulfate may
precipitate out but this will not affect the analysis.
6. Add 1 to 2 drops of Ferroin indicator and stir rapidly on magnetic stirrer while titrating
with standardized 0.10 M FAS.
7. The end point is a sharp color change from blue-green to reddish brown, although the
blue green may reappear within minutes.
8. In the same manner reflux and titrate a blank containing the reagents and a volume of
distilled water equal to that of the sample.
9. COD is given by
COD (mg O2 /L) = [(A-B) M 8000) / (V sample)
REFERENCE MATERIALS:
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1) AWWA, WEF, APHA, 1998, Standard Methods for the Examination of Water and
Wastewater (Methods: 5220 C. Closed Reflux Titrimetric Method)
2) Sawyer, C.N., McCarty, P.L., and Parkin, G.F. 2000. Chemistry for Environmental
Engineering 4th Edition. Tata McGraw-Hill Publishing Company Limited.
Page 6
OBJECTIVES:
To determine Dissolved Oxygen (D.O) concentration in a water sample.
SELECTION OF METHODS
Two methods are commonly used are iodometric method membrane electrode procedure.
Iodometric Method
Azide Modification (For nitrite-N < 0.05 mg/L and Ferrous iron<1 mg/L)
Chemical Reactions:
REAGENTS:
Alkali-iodide-azide Reagent:
a) For saturated or less than saturated samples: Dissolve 500g NaOH (or 700g KOH)
and 150g Kl (or 135g NaI) in distilled water and dilute to 1000mL. Add 10 g sodium
azide, NaN3 dissolved in 40 mL distilled water. This solution should not give colour
with starch solution when diluted and acidified.
b) For supersaturated samples: Dissolve 10g NaN3 in 500mL distilled water. Add
480g NaOH and 750g NaI and stir to dissolve the contents.
Sulfuric acid:
One mL is equivalent to ~ 3mL alkali-iodide-azide reagent.
Starch solution:
Dissolve 2 g laboratory-grade soluble starch and 0.2 g salicyclic acid as
preservative in 100 mL hot distilled water.
Page 8
PROCEDURE
1) Make dilution water by adding 2 mL/L of following reagents in distilled water:
a. Phosphate buffer solution
b. Magnesium sulfate solution
c. Calcium chloride solution
d. Ferric chloride solution
e. Sodium Sulfite solution
2) Collect sample in a BOD bottle using D.O sampler.
3) NOTE: Use separate pipettes of 2 ml capacity for each reagent and take care that tip of
the pipette in each case is dipped well below the liquid surfaces carefully.
a. Add 1mL MnSO4 followed by 1mL of alkali-iodide-azide reagent to a sample
collected in 250 to 300mL bottle up to the brim. The tip of the pipette should be
below the liquid level while adding these reagents. Stopper immediately. Rinse
the pipettes before putting them to reagent bottles.
b. Mix well by inverting the bottle 2-3 times and allow the precipitate to settle
leaving 150 mL clear supernatant. The precipitate is white if the sample is devoid
of oxygen, and becomes increasingly brown with rising oxygen content.
4) At this stage, add 1mL conc. H2SO4.
5) Replace the stopper and mix well till precipitate goes into solution.
6) Take 201 mL of this solution in a conical flask and titrate against std. Na2S2O3 soln.
7) Add 2 drops of starch indicator and continue to titrate till the color of the solution
becomes either colorless or changes to its original sample color.
8) Note down volume of 0.025N sodium thiosulfate consumed.
9) As 1 mL of sodium thiosulfate of 0.025N equals to 1 mg/L dissolved oxygen.
10) Dissolved oxygen (D.O) (in mg/L) = mL of sodium thiosulfate (0.025N) consumed.
Page 9
REFERENCE MATERIAL:
AWWA, WEF, APHA, 1998, Standard Methods for the Examination of Water and
Wastewater
Sawyer, C. N., McCarty, P. L., and Parkin, G. F. 2000. Chemistry for Environmental
Engineering. Fourth Edition, McGraw-Hill, Inc., New York.
Page10
Q2. To determine BOD of a sample, three dilutions of the samples are made (BOD bottle
volume=300mL). In the BOD dilution water (without sample), initial DO=0 (blank). All samples
are incubated at 20C for 5 days. Look at the following data and calculate 5-day BOD value of
the sample at 15C?
t-day BOD= [DOt-DO0]/(P) (1)
where P= Dilution factor = 300mL/(sample volume in mL)
Bottle no. Wastewater sample (mL) Initial DO (mg/L) (DO0) DO at 5-day (mL) (DO5)
1 20 8.9 1.5
2 10 9.1 2.5
3 5 9.2 5.8
4 2 9.2 7.5